Copper-containing trisazo dyestuffs



United States Patent 2,7 05,7 07 1 COPPER-CONTAINING TRISAZO DYESTUFFSErnst Iselin, Dornach, Switzerland, assignor to Sandoz A. G., Basel,Switzerland No Drawing. Application August 11, 1952, SerialNo. 303,821

Claims priority, application Switzerland August 31, 1951 6 Claims. (Cl.260-145) CH: H0 2 l r a NHR wherein R stands for an aryl radical whichmay be a substituted aryl radical, R1 stands for an aryl radical whichmay be substituted by a sulfonic acid substituents, one x stands for asulfonic acid group, the other x stands for hydrogen, y is inortho-position to the -azo'-group and stands for a group capable ofmetal complex formation, z stands for hydrogen, NH2, alkylated NHz,arylated NHz or acylated NI-Iz, and n stands for one of the integers, 1,2, and 3, and wherein the -OH group is in ortho-position and -azois inpara-position to the -azo'-group.

The aforesaid compounds (I) can be prepared by coupling the tetrazocompound from 1 mol of 4,4'-diamino- 1,1'-diphenyl- 3-sulfonic acid, onthe one hand with 1 mol of an aromatic amide of acetoacetic acid, and onthe other hand with 1 mol of an aromatic amine which may be sulfonated,which couples in para-position to the amino group, and which has inortho-position to the amino group agroup which is capable of metalcomplex formation, then further, diazotizing the thus-obtainedaminodisazodyestutf, then coupling the resultant product with 1 mol of ahydroxynaphthalene sulfonic acid of the formula wherein z andn havetheprecedingly-indicated significances, and finally subjecting thethus-prepared trisazo dyestutf to the action of copper-yielding means.

The aforesaid compounds (I) can also be prepared by diazotizing 1 mol of4,4'-diamino-l ,1'-dipheny1-3-su1fonic acid, or the monoacylatedderivative thereof, with 1 mol of an aromatic amide of acetoacetic acid,then saponifying the acylamino group of the 4-amino-4'-acylamino-'l,1-diphenyl3-sulfonic acid moiety (in the case ofthe aforesaidmonoacylated derivative), then further diazotizing the obtained aminoazocompound, then coupling the resultant product with 1 mol of an aromaticamine which may be sulfonated, which couples in para-position to theamino group, and which contains in ortho-position to the amino group agroup which is capable of metal complex formation, then furtherdiazotizing the thus-obtained amino-disazo dyestufi, then coupling thediazotized prodnot with 1 mol of a hydroxynaphthalene derivative of theFormula (II), and finally subjecting the thus-prepared trisazo dyestuffto the action of copper-yielding means.

A further'alternative involves diazotizing 1 mol of a monoacylated4,4-diamino-1,1'-diphenyl-3-sulfonic acid, then coupling .the diazotizedproduct with 1 mol of an 'aromatic amine which may be sulfonated, whichcouples inpara-position to the amino group, and which contains group orby other in ortho-position to the amino group a group which is capableof metal complex formation, then further diazotizing the resultantaminoazo compound, then coupling the diazotized product with 1 mol of ahydroxyphthalene derivative of Formula II, then saponifying theacylamino group of the thus-obtained disazo dyestuif, then diazotizingthe resultant amino-disazo dyestutf, then coupling the diazotizedproduct with 1 mol of an aromatic amide of acetoacetic acid, and finallysubjecting the obtained trisazo dyestuff with copper-yielding means.

Illustrative of the aromatic amides of acetoacetic acid which may beused in preparing the dyestulfs of the present invention are inter alia:

Acetoacetylaminobenzene,

1 -acetoacetylamino-Z-methylbenzene, 1-acetoacetylamino-3-methylbenzene,1-acetoacetylamino-4-methylbenzene, 1-acetoacetylamino-Z-methoxybenzene,1-acetoacetylamino-3-methoxybenzene,

Illustrative of the, aromatic amines which may be sulfonated, whichcouple in para-position to the amino group and which contain inortho-position to the amino group a group which is capable of metalcomplex formation are interalia the following:

l-amino-Z-methoxybenzene, 1-amino-2-methoxy5methylbenzene,1-amino-2,S-dimethoXybenZene, 1-amino-2-methoxynaphthalene, I-amino2-methoxynaphthalene-6-sulfonic acid,l-amino-2-ethoxynaphthalene-o-sulfonic acid, etc.

Where monoacylated 4,4diamino-1,l'-diphenyl-3-sulfonic acid is not used,amines of the type of l-amino-Z methoxy-S-acetylaminobenzem may also heused, T Illustrative of the'hydroxynaphthalene derivativesof Formula IIwhich may be used for the final or intermediate coupling step whenpreparing the dyestuifs ofthe present invention are, among many otherpossible coupling components:

l-hydroxynaphthalene, Z-hydroxynaphthalene,l-hydroxynaphthalene-3-sulfonic acid, 1-hydroxynaphthalene 4-sulfonicacid, l-hydroxynaphthalened-sulfonic acid,1-hydroxynaphthalene-3,6-disu1fonic acid,:1-hydroxynaphthalene-3,8-disulfonic acid, I2-hydroxynaphthalene-4-sulfonic acid, 2-hydroxynaphthalene-6-sulfonicacid, Z-hydroxynaphthalene-7-sulfonic acid,2-hydroxynaphthalene-3,fi-disulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,Z-methylamino-5-hydroxynaphthalene-7-sulfonic acid,2-cyclohexylamino-5-hydroxynaphthalene-7-sulfonic acid,Z-phenylarnino-5-hydroxynaphthalene-7-sulfonic acid, 2 (4' sulfophenylamino) 5 hydroxynaphthalene-7- sulfonic acid, 2 (3 carboxyphenylamino) 5 hydroxynaphthalene-7-sulfonic acid, 2 (4' carboxyphenylamino) 5 hydroxynaphthalene-7-sulfonic acid, v V, I

Z-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-bcnzoylamino-5-hydroxynaphthalene-7-sulfonic acid,Z-amino-S-hydroxynaphthalene-l,7-disulfonic acid, etc.

acid, but may also be carried out in a medium rendered alkaline withsodium carbonate or sodium bicarbonate. The final coupling of thediazodisazo dyestuff with the hydroxynaphthalene sulfonic acid offormula II is advantageously carried out in weak alkaline medium, forexample in a medium rendered alkaline with sodium bicarbonate or withammonia, in the presence of an organic base such, for example, aspyridine or quinoline.

The process is essentially analogously carried out when preparing thedyestuffs of the invention in accordance with the other twoaforedescribed alternative modes of procedure.

Monoacylated 4,4diamino-1,1 diphenyl 3 sulfonic acids which may be usedin preparing the dyestuffs of the present invention comprise, amongothers, the followmg: 4-amino-4'-acetylamino-1,1'-diphenyl-3-sulfonicacid, 4-amino-4-formylamino-1,1-diphenyl-3-sulfonie acid,4-amino-4'-oxalylamino-1,1'-dipheny1-3-sulfonic acid,4-amino-4'-carbethoxy-1,1-diphenyl-3-sulfonic acid, etc.

The saponification of the 4-acylamino group, when this is involved inthepreparation of the new dyestuffs, is advantageously carried out inalkaline medium.

The conversion of the obtained trisazo dyestuffs into the copper complexcompounds thereof may be carried out in various ways, for example byheating in weakly alkaline aqueous medium with ammoniacal copper oxidesolution in the presence or absence of an organic base, or by fusionwith an alkali metal salt of a low molecular aliphatic monocarboxylicacid and a copper salt.

The new dyestuffs dye cellulosic fibers-for example fibers of cotton orregenerated cellulose-4n bright green to olive shades of excellentfastness to washing and of very good fastness to light. They are alsocharacterized by very good exhausting power.

The following examples are illustrative, but not restrictive, of theinvention, setting forth presently preferred embodiments thereof. In thesaid examples, the parts are parts by weight, the percentages arepercentages by weight, and the temperatures are in degrees centigrade.

Example 1 26.4 parts of 4,4-diamino-1,1"diphenyl'3-sulfonic acid aretetrazotized with the aid of 13.8 parts of sodium nitrite. After theaddition of 30 parts of crystalline sodium acetate, a solution of 17.7parts of acetoacetylaminobenzene and 6 parts of sodium hydroxide in 1200parts of water is run in. Upon termination of the formation of theintermediate, the solution is made alkaline with sodium carbonate. Thena solution of 27.5 parts of the sodium salt of1-amino-2-methoxynaphthalene-6-sulfonic acid in 300 parts of water isadded. The obtained disazo dyestuff is isolated, stirred into 1500 partsof water and, after addition of 6.9 parts of sodium nitrite, isdiazotized by pouring into a mixture of 40 parts of concentratedhydrochloric acid in 160 parts of water and ice at -10. Thethus-obtained diazo-disazo dyestuif is filtered off and introduced intoa solution of 31.5 parts 3f2-phenylamino-5-hydroxynaphthalene-7-sulfonic acid and 15 parts ofsodium bicarbonate in 200 parts of water and 200 parts of pyridine. Theresultant trisazo dyestuff is isolated and then coppered in the mannerdescribed in the following paragrap e The isolated trisazo dyestuff isdissolved in 2000 parts of water at -90". After the addition of 10 partsof sodium carbonate, a complex copper solution, prepared by admixing asolution of 25 parts of crystalline copper sulfate in 250 parts of waterwith 45 parts of a 25% aqueous ammonia solution, is added in the courseofv a half hour. The mixture is boiled under reflux for 12 hours, andthe formed dyestuff which corresponds to the formula O--Cu 0 H033 NH mm)is salted out with sodium chloride and then filtered off. It is a darkpowder which dissolves in water'iwith green coloration and inconcentrated sulfuric acid .with brown-olive coloration. It dyescellulosic fibers in bright green shades of outstanding fastness towashing and'of very good fastness to light.

By replacing the 17.7 parts of acetoacetylaminobcnzene by 19.1 parts of1-acetoacetylamino-2'methy1benzene or by 19.1 parts of1-acetoacetylamino-3-methylbenzene or by 19.1 parts of1-acetoacetylainino-4-rriethylbenzene .or by 20.7 parts of1-acetoacetylamino-2 methoxybenzene or by 20.7 parts ofl-acetoacetylamino-l methoxybenzene or by 20.7 parts ofl-acetoacetyl-amino- 4-methoxybenzenc, and otherwise proceeding asprecedingly described in the present example, dyestuffs with similarproperties are obtained.

Likewise, similar dyestuffs are obtained when, while otherwiseproceeding as described in the first two paragraphs of this example, the31.5 parts of Z-phenyI-amino- 5-hydroxynaphthalene-7-sulfonic acid arereplaced by an equivalent amount of2-methylamino-5-hydroxynaphthalene-7-sulfonic acid of2-ethylamino-5-hydroxynaphthalene-7-sulphonic acid or of2'-propylamino-5-hydroxynaphthalene-7-sulfonic acid or of2-(4'-carboxy)- phenylamino-S-hydroxy-naphthalene-7-sulfonic acid or of2-(3-methyl) phenylamino 5 hydroxynaphthalene- 7-sulfonic acid or of2-(4'-methyl)-phenylamino-5-hydroxynaphthalene-7-su1fonic acid or of2-(3'-methoxy)- phen'ylamino-5-hydroxy-naphthalene-7-sulfonic acid: orof 2-(4-methoxy)-phenylamino-5 hydroxynaphthalene- 7-sulfonic acid or of2-cyclohexylamino-5-hydroxy' naphthalene-7-sulfonic acid or of2-propionyl-amino5- l1ydroxynaphthalene-7-sulfonic acid or of2-decanoylamino-5-hydroxy-naphthalene-7-sulfonic acid or of. 2(4-hydroxy-3-carboxy)-phenylamino 5 hydroxynaphthalene-7-sulfonic acidor of 2-(3-hydroxy-4-carhoxy)phenylarnino-S-hydroxynaphthalene-7-sulfonic acid.

Example 2 30 parts of crystalline sodium acetate are added to thetetrazo compound from 26.4 parts of 4,4-diamino- 1,1-diphenyl-3-sulfonicacid, after which a solution of 17.7 parts of acetoacetylaminobenzeneand 6 parts of sodium hydroxide in 1200 parts of water in run in. Uponcompletion of the formation of the resultant intermediate, the solutionis rendered alkaline with sodium carbonate. A solution of 27.5 parts ofthe sodium salt of Lamino- 2-methoxynaphthalene-6-sulfonic acid in 300parts of water is then added. The thus-obtained dyestuff is isolated,stirred into 1500 parts of water and, after the addition of 6.9 parts ofsodium nitrite, is diazotized by pouring into an ice-cold aqueoussolution containing 40 parts of concentrated hydrochloric acid at 5-10.The resultant diazo-disazo dyestuff is filtered off and intro duced intoa solution of 31.9 parts of 2-amino-5-hydroxynaphthalene-l,7-disulfonicacid and 30 parts of sodium bicarbonate in 200 parts of water and 200parts of pyridine. The resultant trisazo dyestuff is isolated and thencoppered in the manner described in the following paragraph.

The trisazo dyestufi of the preceding paragraph, in the form of a moist,but well-pressed filter cake is warmed with 350 parts of crystallinesodium acetate and 50 parts of crystalline copper sulfate until ahomogeneous melt OOH water distills offis reached. The whole is thenfiltered oil. and dried. It dissolves in water with a green coloration,and with olive coloration in concentrated sulfuric acid, and dyes cottonand fibers of regenerated cellulose in green shades of very goodfastness to light and to washing.

it, while otherwise proceeding as described in the foregoing twoparagraphs, the 31.9 parts of 2-amino-S-hydroxynaphthalene-l,7-disulfonic acid are replaced by 39.5 parts of2-(4'-sulfophenylamino)-5hydroxynaphthalene-7-sulfonic acid or by 35.9parts of 2-(3-carb0xyphenylamino)--hydroxynaphthalene-7-sulfonic acid orby 30.4 parts of 1-hydroxynaphthalene-3,6-disulfonic acid or by 30.4parts of l-hydroxynaphthalene-3,8-disulfonic acid or by 30.4 parts of2-hydroxynaphthalene-3,6-disulfonic acid, dyestutfs of similarproperties are obtained.

Example 3 26.4 parts of 4,4-diamino-1,1'-diplienyl-3-sulfonic acid aretetrazotized with the aid of 13.8 parts of sodium nitrite. After theaddition of 30 parts of crystalline sodium acetate, a solution of 24.3parts of the sodium salt of 1-acetoacetylaminobenzene-4 carboxylic acidand 6 parts of sodium hydroxide in 1200 parts of water, is run in. Uponcompletion of the formation of the resultant intermediate, the solutionis adjusted to alkalinity by means of sodium carbonate. Then a solutionof 27.5 parts of the sodium salt ofl-amino-Z-methoxynaphthalene-6-sulfonic acid in 300 parts of water isadded. The obtained disazo dyestuif is isolated, stirred into 1500 partsof water and, after addition of 6.9 parts of sodium nitrite, isdiazotized by pouring into a mixture of 40 parts of concentratedhydrochloric acid in 200 parts of water and ice at 510. Thethus-produced diazo-disazo dyestutf is filtered off and introduced intoa solution of 23.9 parts of Z-amino-S-hydroxynaphthalene-7-sulfonic acidand parts of sodium bicarbonate in 200 parts of water and 200 parts ofpyridine. The resultant trisazo dyestuff is isolated and then copperedin-the manner described in the following paragraph.

The trisazo'dyestuflf, obtained according to the preceding paragraph, isdissolved in 2000 parts of water at 85-90. After the addition of 10parts of sodium carbonate, a complex copper solution, prepared byadmixing a solution of 25 parts of crystalline copper sulfate aqueous isadded in the course of a half hour.

is salted out with sodium chloride and filtered off. It is a dark powderwhich dissolves with green coloration in water and with blue-greencoloration in concentrated sulfuric acid. It dyes celulosic fibers inbright olive shades of outstanding fasteness to washing and of very goodfastness to light. g

If, while otherwise proceeding according to the pre- H028 -NH2 cedingtwo paragraphs, the 24.3 parts of the sodium salt of1-acetoacetylaminobenzene-4-carboxylic acid are replaced by 25.9 partsof the sodium salt of l-acetoacetylamino-4-hydroxybenzene-3-carboxylicacid or by 25.9 parts of the sodium salt of1-acetoacetylamino-3-hydroxybenzene-4-carboxylic acid and/or the 23.9parts of 2- amino-S-hydroxynaphthalene-7-sulfonic acid] are replaced by34.3 parts of 2-benzoylamino-5-hydroxynaphthalene- 7-sulfonic acid or by28.1 parts of 2-acetylamino-5- hydroxynaphthalenc-7-sulfonic acid,dyestuffs which yield dyeings of similar shades and which have similarfastness properties are obtained.

Example 4 26.4 parts of 4,4'-diamino-l,l'-diphenyl-3asulfonic acid aretetrazotized with the aid of 13.8 parts of sodium nitrite. The tetrazosolution is adjusted to weak alkalinity with sodium bicarbonate, andthen a solution of 17.7 parts of acetoacetylaminobenzene in 2000 partsof water is slowly run in. When the formation of intermediate product isover, the solution is adjusted to alkalinity with sodium carbonate. Thena solution of 28.9 parts of the sodium salt of2-ethoxy-l-aminonaphthalene-6-sulfonic acid in 300 parts of water isadded. The obtained disazo dyestutf is isolated, stirred into 1500 partsof water and, after the addition of 6.9 parts of sodium nitrite,diazotized at 5-l0 by pouring into an ice-cold aqueous solutioncontaining 40 parts of concentrated hydrochloric acid. The thus-obtaineddiazo-disazo dyestufi is filtered off and introduced into a solution of22.4 parts of 1-hydroxy-naphthalene-4-sulfonic acid and 15 parts ofsodium bicarbonate in 200 parts of water and 200 parts of pyridine. Theresultant trisazo dyestuff is isolated and then coppered in the mannerdescribed in the following paragraph.

The said trisazo dyestufr", as obtained according to the preceding at8590. -Tnen, sodium carbonate, a complex copper solution, prepared byadmixing a solution of 25 parts of crystalline copper sulfate in 250parts of water with 45 parts of a 25% aqueous ammonia solution, is addedin the course of a half hour. The whole is then boiled under reflux for12 hours, the product salted out with sodium chloride,

paragraph, is dissolved in 2000 parts of water 1 after the addition of10 parts of' 7 nd. the. Preci it te e fi hi h c r espond to. e z-methxybenzai a e repla ed y .5-3 par s of lformula, 2.5;:diqrfihoxvbenzen fby Par f m. --Qu,. O

NH-C o-o H N=N -N=N N;N

0 1 A) SOBH filtered off. It is a dark powder which dissolves withmethoxynaphthalene or by 18.7 parts of l-amino-2- green coloration inwater and with brown-olive coloraethoxynaphthalene or by 12.3 parts ofl-amino-Z- tion in concentrated sulfuric acid. It dyes cotton andmethoxybenzene or by 18.0 parts of l-amino-Z-methoxyfibers ofregenerated cellulose in bright yellowish green S-acetylaminobenzene,dyestuffs of similar shades and oi shades of very good fastness to lightand to Washing. like properties are obtained.

If, while otherwise proceeding as previously described Exam le 6 in thepresent example, the 17.7 parts of acetoacetylp aminobenzene arereplaced by 25.7 parts of l-aceto- 00 28.6 parts of the sodium salt of4,4'-diamino-1,l'- acetylami'nobenzene-3-sulfonic acid or by 25.7 par-tsof di-phenyl-ZBssuIfonic acid are dissolved in 800. parts ofl-acetylaminobenzene-4-sulfonic acid or by 28.7 parts Water. Afterthe'addition of 6.9. parts of sodium nitrite, ofl-acetoacetylamino-2-methoxybenzene-4-sulfonic acid 40. parts of glacialacetic acid arerun in at 10 and the and/or the 22.4 parts of1-hydroxynaphthalene-4-sulmixture stirred until diazotization iscomplete. The fonic acid are. replaced by 22.4 parts of2-hydroxynaphdiazo solution is poured into a solution of; 17.71 parts ofthalene-4-sulfonic acid or by 22.4 parts of 2-hydroxyaeetoacetylaminobenzene and 6. parts of sodium hydrox-.

naphthalene-6ssulfonic acid, dyestuffs of similar propide in 600 partsof water. Upon completion of the erties are obtained. coupling whichtakes place, the resultant dyestulf is Exam le isolated, then stirredinto 1200 parts of water and, after m, the addition of 6.9 parts ofsodium nitrite, diazotized 30 parts of crystalline sodium acetate areadded to at 510 by pouring into a mixture of 40 parts of conthe tetrazocompound from 26.4 parts of 4,4'-diamino centrated hydrochloric acid in200 parts of a mixture of l,l-diphenyl-3-sulfonic acid, and then asolution of 43.0 Water and ice. The thus-obtained diazo-monoazo comparts of the sodium salt of 2-acetoacetylaminonaphthapound is run, at10", into a solution of 27.5 parts of the lene-5,7-disulfonic acid in1200 parts of water is run sodium salt ofl-amino-2-methoxynaphtha1ene6-sulfonie in. Upon completion of theresultant intermediate acid and parts of sodium carbonate in 300 partsof formation, the solution is made acid with acetic acid, water. Uponcompletion of the coupling, the dyestui'f and a solution of 13.7 partsof l-ammo-S-methyl-Z- is isolated and further Worked u as described inExmethoxybenzene and 12 parts of concentrated hydroample 2.

chloric acid in 200 parts of water is added dropwise. 40 Thethus-prepared dyestuff has properties similar to When the thus-initiatedcoupling is finished, the reaction those described in Example 2 Itcorresponds to the mass is adjusted to alkalinity with sodium carbonate,formula O.--Cl1 Q \\A l NIL-O o-o HN=N.-C -C N=N .N=- N- 03H HOsS-- NH2CH: l I

S OsH 5 03 the formed disazo dyestufi isolated, stirred; into 1500, I I7 parts of water and, after addition of 6.9 parts of sodium nitrite,diazotized by pouring into a mixture of 40 parts 30; parts. ofcrystalline sodium acetate are added to the of concentrated hydrochloricacid in 240 parts of water tctrazo, compound from 2 6,4 parts of4,4-diamino-l,l;- and ice at 510. The thus-obtained diazo-disazodyediphenyl-3-sulfonic acid, and then a solution of 43.0 parts stuff isfiltered off and then introduced into. a solution or the sodium salt ofZ-acetoacetylamino-naphthaleneof 22.4 parts of1hydroxynaphthalenei:sulfouic acid 5,7-d1sulfonic acid in 1200 parts ofwater is run in. Upon and 15. parts of sodium' bicarbonate in 200; partsof Water completion of the resultant intermediate formation. the and 200parts of pyridine. The resultant trisazov dye; 0 solution is renderedalkaline, with sodium carbonate. A stulf is isolated and then coppered121' the manner de-.. solution of 27.5, par-ts of the sodium salt of1"clfl1i110"2' scribed in. the following paragraph.methoxy-uaphthalene-dtsulfonic acid. in 300. par-ts of wa- The aforesaidtrisazo dyestutf is dISSOlVfiddl] 2000 parts. ter 18 then added. Theresultant disazo dyestufi? is iso:

of water at 80-9.0. fter the addition of: 10 parts. of lated, stirredinto 1500 parts of waterand, after the addisodium. carbonate, a complexcopper solution, prepared 5 tron of 6.9 parts of sodium nitrite, isdiazotiz ed at 5Tl0 by admixing a solution of 25' parts of crystallinecopper by pouring into a mixture of 40, parts of concentrated. sulfatein 250 parts of water with parts of a 25% hydrochloric acid in 200 partsof a'mixture of water and aqueous ammonia solution, is added in the,course of a ice. The now-present diazo disazo dyestuff is filtered halfhour. The mixture is boiled under reflux for 12 off and introduced intoa solution of 16.6 parts. of the, hours, and the formed dyestuff whichcorresponds, to the, sodium. salt of 2 -.l 1ydroxynaphthalene and 15parts of. formula sod um bicarbonate in 200. parts of water and 200.parts notsrun-o Q CH-N= N 5,0311 l- H038 0. g. is salted out with sodiumchloride and filtered off. The of: pyridine, whereupon couplingtakesplace., The result. dyestufl is a darkpowder which dissolves withgreen ant trisazo 'dyest if is isolated and then coppered in the.coloration in water. It dyes cellulosic fibers in green manner describedin the followingparagraph. shades of very good fastness properties. Thetriazo dyestuff, obtained as described in the pre-v while otherwise,proceeding as aforedescribed inj ceding, paragraph, is dissolved in 2000parts ofwater' at the; resent example, the 13.7 parts; of l-amno-.."w':-1nethyl;v 80-90? Afterthe addition of 10 parts of sodium can.

bonate, a copper complex solution, prepared by admixing a solution of 25parts of crystalline copper sulfate in 250 parts of water with 45 partsof a 25% aqueous ammonia solution, is run within the course of a halfhour. The resultant mixture is then boiled under reflux for 12 hours,and the thus-formed dyestuff which corresponds to the formula colorationin water and which dyes cellulosic fibers in olive-green shades of verygood fastness to washing and to light.

Example 8 26.4 parts of 4,4'-diamino-l,1'-diphenyl-3-sulfonic acid aretetrazotized with the aid of 13.8 parts of sodium nitrite. After theaddition of 30 parts of crystalline sodium acetate, a solution of 43.0parts of the sodium salt .of 2 acetoacetylaminonaphthalene 5,7disulfonic acid in 1200 parts of water is run in. Upon completion of theresultant intermediate formation, a solution of 28.9 parts of the sodiumsalt of 1-amino-2-ethoxynaphthalene-6'sulfonic acid in 300 parts ofwater is added to the reaction mass. The pH of the solution ismaintained between 4. and 4.5 by the addition of sodium acetate. Thethus-' produced disazo dyestufl' is filtered oif, stirred'into 1500parts of water and 40 parts of concentrated sodium hydroxide solutionand, after the addition of 6.9 parts of sodium nitrite, is diazotized at5-10 by pouring into a mixture of 75 parts of concentrated hydrochloricacid and 200 parts of a mixture of water and ice. The isolateddiazo-disazo dyestuff is introduced into a solution of 3413 parts of2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid in parts ofconcentrated aqueous ammonia solu; tion, 200 parts of water and 200parts of pyridine, where'- upon formation of trisazo dyestuff takesplace. The latter is isolated and converted into the copper complexcompound thereof. This is carried out after the manner described in'the'second paragraph of Example 1 or of Example 2. The

sponds to the formulaof outstandinglfastness to washingcuprlferoustrisazo dyestufi-which correand fibers of regeneratedcellulose-- carbethoxy-1,1 '-diphenyl-3-sulfonic oxy)-benzoylamino-5hydroxynaphthalene 7 sulfonic The diazo compound from 30.6acetylamino-1,1-diphenyl-3-sulfonic parts of 4-amino-4'-, acid is addedto a sour solution of 27.5 parts of the sodium salt of l-amino-2-methoxy-naphthalene-6-sulfonic acid in 300 parts of water. The pH of thesolution is maintained between 4 and 4.5 by the addition of sodiumacetate or sodium formate until the coupling is completed. The formedmonoazo dyestuff is isolated, dissolved in 600 parts of water containing40 parts of concentrated sodium hydroxide solution and, after theaddition of 7.0 parts of sodium nitrite, diazotized at 510 by pouringinto a mixture of parts of concentrated hydrochloric acid and 200 partsof a mixture of water and The resultant diazo-azo sodium carbonate arethen added and the mixture stirred at 5 until the further coupling whichensues is completed. The formed disazo dyestufl is isolated, and then,in order to saponify the 4-acetylamino group, stirred into 1000 parts ofwater and, after the addition of 100 parts of concentrated sodiumhydroxide solution, stirred at -90 until complete saponification hasbeen achieved. 7 parts of sodium nitrite are then added, anddiazotization effected at 5-10" by pouring the reaction mass into amixture of 150 parts of concentrated hydrochloric acid and 200 parts ofice. The resultant diazo-disazo dyestuif is isolated and is added to asolution of 43.0 parts of the sodium salt ofZ-acetoacetylamino-naphthalene-S,7- disulfonic acid, 500 parts of waterand 200 parts of pyridine, whereupon trisazo dyestufi formation takesplace. The trisazo dyestutf is isolated and converted into the coppercomplex after the manner described in the second paragraph of Example 1or 2. The cupriferous dyestufi' which corresponds to the formula SOQH isa dark powder which possesses properties similar to those of the productdescribed in Example 7.

Example 10 The diazo compound from 33.6 parts of 4-amino-4- acid isadded to a solution of 43.0 parts of the sodium salt of2-acetoacetylaminonaphthalene-5,7-disulfon1c acid, 30 parts of concen--bromo)-benzoylaminoor dium hydroxide solution are added trated sodiumhydroxide solution, 10 parts of sodium carbonate and 400 parts of water.Upon completion of the coupling whichensues, 80 parts of concentratedsoand the whole is amass? tion, followed by a solution of 275 parts ofthe sodium salt of 1-a mino-2-methoxynaphtha1enerfi-sulfonic acid in 300parts of Water. The mixture is stirred at. 5-10 until the coupling whichensues is completed, the mixture. then made alkaline by the addition of40 parts of concentrated sodium hydroxide solution, 7.0 parts of sodiumnitrite added, and further diazotization carried out by pouring thereaction mixture into a mixture of 75, parts of con- 'When centratedhydrochloric acid and; 200 parts of ice.

l CH3 h s diaz z i h un. o eomp e om. e d a oisazo dyestuif is filteredoff and introduced at 5 ,l into a solution of 34.3 parts ofZ-benzoylamino--hydroxynaphthalene-7-sulfonic, acid in parts ofconcentrated aqueous ammonia solution, 200 parts of pyridine basemixture, whereupon trisazo dyestuti formation takes place. The dyestufiis isolated and converted, into the copper complex compound by themethod disclosed in paragraph 2 of Example l or Example 2. Thecupriferous dyestuft which corresponds. to

the formula O O l "arts of water and 20 0, 35

1.2 Example. 11

pa ts oteot o are in er ed n a ye a h con ai ing 100 parts of lime-freewater at Then a concentrated aqueous solution, containing 0.1 part of a.dyestuff, corresponding to formula III supra and which may be re-.placed by 0,1 part of any of the cupriferous dyestuff products of theother examples), is added to the bath which is thereupon heated toboiling in the. course of a half hour, the boiling temperature beingthen maintained for a further half hour. In the course of the dyeingprocess, 0.5 to 2 parts of Glauber salt are added in the form of aconcentrated aqueous solution. Upon completion of the dyeing, thematerial is allowed to remain in the gathd until it cools to 50,whereupon it is rinsed and Having thus disclosed the invention what isclaimed is:

copper ompl x. omp und f,- a r azo dyestuffyvhichlcorre'sponds in itscopper-tree form to the general ormu akyl and NH .CO.mono-nuclear aryl,and it is one of the integers l, 2 and 3, and; wherein OH stands inorthoposition and -azo.- in para-position to -azo'-.

2. The copper complex compound which corresponds to the formula 3. Thecopper complex compound which corresponds 7 to the formula 4. The coppercomplex compound which corresponds to the formula OCH 5. The coppercomplex compound which corresponds 15 to the formula 6. The coppercomplex compound which corresponds to the formula References Cited inthe file of this patent UNITED STATES PATENTS 1,851,121 Stusser Mar. 29,1932 2,282,331 Krebser et al May 12, 1942

1. A COPPER COMPLEX COMPOUND OF A TRISAZO DYESTUFF WHICH CORRESPONDS INITS COPPER-FREE FORM TO THE GENERAL FORMULA